Rambutan-like ZnCo2O4 microsphere was successfully synthesized on foam nickel (NF) by facile low-temperature hydrothermal method. The unique structure is composed of nanorods by self-assembly, eventually resulting in a porous hierarchical structure consisting of microspheres in the center and spiny nanorods growing outward. The specific capacity of ZnCo2O4/NF remains at 877.91 mAh g−1 after 400 cycles with a current density of 0.2 A g−1 and 723.33 mAh g−1 at a current density of 1 A g−1 in the rating performance. Its excellent cycling and rating performance is attributed to its unique hierarchical mesoporous structure and high carrier transport efficiency. In addition, the hierarchical structure improves the pseudo-capacitance effect at the electrode interface, enhancing the additional reversible capacity and charge/discharge capability.